KR102782219B1 - Method for forming a silicon-containing film, and composition and silicon precursor compound used therefor - Google Patents

Abstract

By using a composition for forming a silicon-containing film including a silicon precursor compound represented by chemical formula 1, a silicon-containing film including a silicon-containing oxide film or a silicon-containing composite metal oxide film can be efficiently formed at a high temperature of 600°C or higher, and the film thickness and composition can be controlled as desired, and a silicon-containing film having excellent covering properties and uniformity can be formed even on a substrate having a complex shape.

Description

METHOD FOR FORMING A SILICON-CONTAINING FILM, AND COMPOSITION AND SILICON PRECURSOR COMPOUND USED THEREFOR

The present invention relates to a method for forming a silicon-containing film, a composition used therefor, and a silicon precursor compound. Specifically, the present invention relates to a method for forming a silicon-containing film at a high temperature of 600° C. or higher using a composition for forming a silicon-containing film including a silicon precursor compound having a specific structure, a silicon-containing film formed thereby, a composition used therefor, and a silicon precursor compound.

Silicon-containing films are one of the thin films that are essential for operating semiconductors such as DRAM, flash memory, resistive memory (ReRAM), or phase-change memory (PCRAM), as well as non-semiconductor devices such as logic devices.

As such silicon-containing films, silicon-containing oxide films have the characteristic of fast deposition rates, whereas silicon-containing nitride films have the characteristic of slow deposition rates. For various applications, a silicon-containing film that can be selectively deposited only at a desired location is required.

In addition, as the development of products with complex shapes such as high aspect ratios and three-dimensional structures is diversified in the semiconductor and non-semiconductor fields, there is a demand for a composition for forming a silicon-containing film including a silicon precursor compound that can be used in atomic layer deposition (ALD), which is suitable for process temperatures for various applications and can overcome high step ratios.

In particular, it is important to exhibit self-limiting film growth characteristics in order to overcome the step ratio that may occur due to high integration and scale down of devices.

Accordingly, there is a need for various developments regarding a film-forming composition including a silicon precursor compound that is suitable for ALD, forms a uniform and dense film, exhibits stress-resistant properties, and has self-limiting film growth properties even at high temperatures of 600°C or higher, and a method for forming a silicon-containing film using the same.

Republic of Korea Registered Patent No. 10-0734393

The technical problem to be solved by the present invention is to provide a method for forming a silicon-containing film at a high temperature of 600°C or higher using a composition for forming a silicon-containing film including a silicon precursor compound having a specific structure, and a silicon-containing film formed thereby.

Another technical problem to be solved by the present invention is to provide a silicon precursor compound having a specific structure.

Another technical problem to be solved by the present invention is to provide a method for producing the silicon precursor compound.

Another technical problem to be solved by the present invention is to provide a composition for forming a silicon-containing film comprising the silicon precursor compound.

However, the problems to be solved by the present invention are not limited to the problems mentioned above, and other problems not mentioned will be clearly understood by those skilled in the art from the description below.

The present invention provides a method for forming a silicon-containing film, comprising the step of depositing a silicon-containing film using a composition for forming a silicon-containing film, which comprises a silicon precursor compound represented by the following chemical formula 1:

[Chemical Formula 1]

In the above chemical formula 1,

R ₁ and R ₂ are each independently selected from the group consisting of hydrogen and linear or branched C ₁ -C ₄ alkyl groups, or

R ₁ and R ₂ are directly or indirectly linked to each other to form a substituted or unsubstituted C ₄ -C ₉ cyclic group, wherein the C ₄ -C ₉ cyclic group contains 1 or 2 nitrogens (N) and 0 to 2 oxygens (O).

In addition, the present invention provides a composition for forming a silicon-containing film, which comprises a silicon precursor compound represented by the chemical formula 1 and is used for depositing a silicon-containing film.

In addition, the present invention provides a silicon-containing film formed by the method for forming the silicon-containing film.

Furthermore, the present invention provides a silicon precursor compound represented by the following chemical formula 0 or the following chemical formula 1:

[Chemical formula 0]

[Chemical Formula 1]

In the above chemical formula 1,

R ₁ and R ₂ are each independently selected from the group consisting of hydrogen and linear or branched C ₁ -C ₄ alkyl groups, or

R ₁ and R ₂ are directly or indirectly linked to each other to form a substituted or unsubstituted C ₄ -C ₉ cyclic group, wherein the C ₄ -C ₉ cyclic group contains 1 or 2 nitrogens (N) and 0 to 2 oxygens (O).

A method for forming a silicon-containing film according to one embodiment of the present invention can efficiently form a silicon-containing film including at least one selected from the group consisting of a silicon-containing oxide film and a silicon-containing composite metal oxide film at a high temperature of 600° C. or higher using a silicon-containing film forming composition including a silicon precursor compound having a specific structure, and can control the thickness and composition of the film to a desired thickness and composition, and can form a silicon-containing film having excellent covering properties and a uniformity even on a substrate having a complex shape.

In particular, the method for forming a silicon-containing film of the present invention can be applied to various fields such as a moisture penetration prevention film for memory devices, logic devices, display devices, and organic light-emitting diode (OLED) devices, and since a film having a desired thickness can be obtained at a high temperature of 600°C or higher during film deposition, it can be very effectively utilized in electronic devices requiring excellent film properties and covering properties.

FIG. 1 is a graph showing the deposition characteristics of a silicon-containing oxide film according to a temperature of 600° C. to 850° C. when depositing a silicon-containing film using a composition for forming a silicon-containing film including the silicon precursor compounds of Examples 1 and 3 and Comparative Examples 1 and 2 of the present invention.
FIG. 2 is a graph showing the results of secondary ion mass spectrometry (SIMS) of a silicon-containing oxide film deposited at 750° C. using a composition for forming a silicon-containing film including the silicon precursor compound of Example 3 and Comparative Example 1 of the present invention.
FIG. 3 is a transmission electron microscope (TEM) image showing step coverage confirmed by depositing a silicon-containing film-forming composition including the silicon precursor compounds of Examples 1 and 3 of the present invention and Comparative Example 1 on a patterned wafer at 750° C.
FIG. 4 is a transmission electron microscope (TEM) image showing the step coverage confirmed by depositing a silicon-containing film-forming composition including the silicon precursor compound of Example 3 and Comparative Example 1 of the present invention on a patterned wafer at 650° C.

The present invention is described in more detail below.

The advantages and features of the present invention, and the method for achieving them, will become clear with reference to the embodiments described below. However, the present invention is not limited to the embodiments disclosed below, but may be implemented in various different forms, and these embodiments are provided only to make the disclosure of the present invention complete and to fully inform a person having ordinary skill in the art to which the present invention belongs of the scope of the invention, and the present invention is defined only by the scope of the claims.

Additionally, when it is said in this specification that a part is "on" another part, this includes not only cases where it is "directly on" the other part, but also cases where there is another part in between.

In this specification, when a part is said to "include" a certain component, this does not mean that other components are excluded, but rather that other components may be included, unless otherwise specifically stated.

All numbers and expressions indicating the amounts of ingredients, reaction conditions, etc. described in this specification should be understood as being modified by the term "about" in all cases unless otherwise specified.

In this specification, the terms “film” or “thin film” respectively, unless specifically distinguished, mean both “film” and “thin film”.

As used herein, the term "alkyl" or "alkyl group" includes linear or branched alkyl groups and all possible isomers thereof. For example, the alkyl or alkyl group may include, but is not limited to, a methyl group (Me), an ethyl group (Et), a n-propyl group ( ⁿ Pr), an isopropyl group ( ⁱ Pr), a n-butyl group ( ⁿ Bu), an isobutyl group ( ⁱ Bu), a tert-butyl group (tert-Bu, ^t Bu), a sec-butyl group ( ^sec Bu), and the like, as well as isomers thereof.

[Method for forming a silicon-containing film]

According to one embodiment of the present invention, a method for forming a silicon-containing film is provided, comprising the step of depositing a silicon-containing film using a composition for forming a silicon-containing film, the composition including a silicon precursor compound represented by the following chemical formula 1:

[Chemical Formula 1]

In the above chemical formula 1,

R ₁ and R ₂ are each independently selected from the group consisting of hydrogen and linear or branched C ₁ -C ₄ alkyl groups, or

R ₁ and R ₂ are directly or indirectly linked to each other to form a substituted or unsubstituted C ₄ -C ₉ cyclic group, wherein the C ₄ -C ₉ cyclic group contains 1 or 2 nitrogens (N) and 0 to 2 oxygens (O).

As an example, in the chemical formula 1, R ₁ and R ₂ can each be independently selected from the group consisting of hydrogen, a methyl group, an ethyl group, a normal propyl group, an isopropyl group, a normal butyl group, an isobutyl group, a tert-butyl group, and a sec-butyl group.

As another example, in the above formula 1, R ₁ and R ₂ are directly or indirectly connected to each other (together with the N atom to which they are bonded) to form a substituted or unsubstituted C ₄ -C ₉ cyclic group, wherein the cyclic group may contain one or two nitrogens (N) and zero to two oxygens (O). Specific examples of the C ₄ -C ₉ cyclic group include an azetidinyl group, a pyrrolidinyl group, a piperidinyl group, a piperazinyl group, a morpholinyl group, and an azepanyl group. The C ₄ -C ₉ cyclic group may have one or more, for example, 1 to 3, substituents. The substituent that the above C ₄ -C ₉ cyclic group may have may be, for example, one or more selected from the group consisting of a C ₁ -C ₆ alkyl group, a halogen element (F, Cl, Br, I), a hydroxyl group (OH), and a C ₁ -C ₆ alkoxy, but is not limited thereto.

Specifically, the method for forming the silicon-containing film may include a step of depositing a silicon-containing film on a substrate by chemical vapor deposition (CVD) or atomic layer deposition (ALD) using a composition for forming a silicon-containing film including a silicon precursor compound represented by the chemical formula 1. The silicon-containing film may include at least one selected from the group consisting of a silicon-containing oxide film and a silicon-containing composite metal oxide film. The deposition may be performed at a temperature of 600° C. or higher, specifically, 600° C. to 850° C.

In one specific example, the silicon-containing film can be formed by chemical vapor deposition (CVD) or atomic layer deposition (ALD) at a temperature of 600° C. to 850° C.

According to a method for forming a silicon-containing film according to one embodiment of the present invention, a silicon-containing film comprising at least one selected from the group consisting of a silicon-containing oxide film and a silicon-containing composite metal oxide film can be efficiently formed at a high temperature of 600° C. or higher using a silicon-containing film forming composition including a silicon precursor compound having a specific structure represented by the chemical formula 1, and the silicon-containing film can be controlled to have a desired thickness and composition, and a silicon-containing film having excellent covering properties and a uniformity can be formed even on a substrate having a complex shape.

In particular, the method for forming a silicon-containing film of the present invention can be applied to various fields such as memory devices and logic devices, display devices, and moisture penetration prevention films for organic light-emitting diode (OLED) devices, and has technical significance in that a film of a desired thickness can be obtained at a high temperature of 600°C or higher during film deposition.

In addition, the present invention provides a composition for forming a silicon-containing film, which comprises a silicon precursor compound represented by the chemical formula 1 and is used for depositing a silicon-containing film by chemical vapor deposition (CVD) or atomic layer deposition (ALD) at a temperature of 600°C or higher, wherein the silicon-containing film comprises at least one selected from the group consisting of a silicon-containing oxide film and a silicon-containing composite metal oxide film.

Specifically, in the method for depositing the silicon-containing film, the formation of the silicon-containing film may include a step of depositing the silicon-containing film on a substrate (substrate) using a composition for forming a silicon-containing film including a silicon precursor compound represented by the chemical formula 1.

The above substrate may be, but is not limited to, a silicon semiconductor wafer, a compound semiconductor wafer, or a plastic substrate (PI, PET, PES). In addition, a substrate having holes or grooves may be used, and a porous substrate having a large surface area may be used.

In particular, a silicon-containing film having a thickness of several nanometers (nm) to several micrometers (㎛) can be uniformly formed on a substrate having a pattern (groove) on the surface, a porous substrate, or a plastic substrate at a temperature range of 600℃ or higher, specifically, 600℃ to 850℃, and has an excellent effect of being able to form a silicon-containing film with a uniform thickness on the entire surface of the substrate including the surface of the deepest part of a fine pattern (groove) having an aspect ratio of 1 or higher, for example, about 1 to 50 or higher, and a width of 1 ㎛ or less, for example, about 1 ㎛ to 10 nm or less, and the surface of the fine unevenness (groove). For example, the silicon-containing film can be formed on a substrate including one or more unevennesses having an aspect ratio of 1 or higher and a width of 1 ㎛ or less.

The method for depositing the above silicon-containing film can utilize methods, devices, etc. known in the technical field of the present invention, and, if necessary, can be performed using one or more additional reaction gases.

The deposition method of the above silicon-containing film can be performed by CVD, such as metalorganic chemical vapor deposition (MOCVD), or ALD. The MOCVD or ALD can be performed using a deposition apparatus, deposition conditions, and reaction gas known in the art.

Specifically, after accommodating a substrate in the reaction chamber, a silicon-containing film-forming composition including the silicon precursor compound is transported onto the substrate using a carrier gas or a diluting gas to deposit a silicon-containing film at a high deposition temperature of 600° C. or higher, specifically, 600° C. to 850° C.

Here, the deposition temperature within the above range can be applied to memory devices, logic devices, display devices, etc., and since the process temperature is wide, it has a high applicability in various fields, and in particular, by using a composition for forming a silicon-containing film including a compound in the silicon bulb that is strong against a dense film and stress at high temperatures, deposition is easy within the above range of deposition temperatures.

In addition, it is preferable to use at least one mixed gas selected from the group consisting of argon (Ar), nitrogen (N ₂ ), helium (He), and hydrogen (H ₂ ) as the carrier gas or diluting gas.

In addition, the method for forming the silicon-containing film may include a step of supplying the silicon precursor compound into the reaction chamber using a method including at least one selected from the group consisting of a bubbling method, a liquid delivery system (LDS) method, a vapor flow control (VFC) method, and a bypass method.

Specifically, the method for supplying the silicon precursor compound into the reaction chamber may use at least one method selected from the group consisting of a bubbling method in which a silicon-containing film-forming composition including the silicon precursor compound is forcibly vaporized using a carrier gas or a diluting gas; a liquid supply system (LDS) method in which a liquid is supplied at room temperature and vaporized through a vaporizer; a gas flow control (VFC) method in which the vapor pressure of the precursor is used to directly supply the composition; and a bypass method in which vaporization is performed by heating.

For example, when the vapor pressure is high, a gas flow rate control method can be used, when the vapor pressure is low, a bypass method for heating and vaporizing the container can be used, or a bubbling method using argon (Ar) or nitrogen (N ₂ ) gas can be used to supply the silicon-containing film-forming composition including the silicon precursor compound into the reaction chamber.

In one specific example, the step of supplying the silicon precursor compound into the reaction chamber can be performed using a carrier gas or a dilution gas in a temperature range of 0.1 torr to 10 torr and room temperature to 150° C.

More specifically, the supply method includes a bubbling method or a bypass method, and the bubbling method is performed using a carrier gas or a dilution gas in a temperature range of 0.1 torr to 10 torr and room temperature to 150°C, and the bypass method can be performed using a vapor pressure of 0.1 torr to 1.5 torr in a temperature range of room temperature to 100°C. For example, the supply of the composition for forming a silicon-containing film including the silicon precursor compound into the reaction chamber can be performed using a carrier gas or a dilution gas in a temperature range of 0.1 torr to 10 torr and room temperature to 100°C.

In addition, in order to vaporize the composition for forming a silicon-containing film including the silicon precursor compound, it can be transported by, for example, argon (Ar) or nitrogen (N ₂ ) gas. Or, during deposition, thermal energy or plasma can be used, or a bias can be applied to the substrate.

Meanwhile, in order to deposit at least one silicon-containing film selected from the group consisting of a silicon-containing oxide film and a silicon-containing composite metal oxide film according to the method for forming the silicon-containing film, at least one selected from the group consisting of water vapor (H ₂ O), oxygen (O ₂ ), oxygen plasma (O ₂ Plasma), hydrogen peroxide (H ₂ O ₂ ), and ozone (O ₃ ) may be used during the deposition.

The at least one silicon-containing film selected from the group consisting of the silicon-containing oxide film and the silicon-containing composite metal oxide film may include, for example, at least one selected from the group consisting of HfSiO _x , ZrSiO _x , _{TiSiO x ,} HfAlO _x , ZrAlSiO _x , TiAlSiO _x , ZrHfSiO x , ZrHfAlSiO _x , SiC and SiCO, but is not limited thereto. In this case, x may be 1 to 3.

A composition for forming a silicon-containing film comprising a silicon precursor compound represented by the above chemical formula 1 is described in more detail below.

[Composition for forming a silicon-containing film]

The present invention provides a composition for forming a silicon-containing film comprising a silicon precursor compound represented by the chemical formula 1.

Specifically, the composition for forming the silicon-containing film includes a silicon precursor compound represented by the chemical formula 1, and can be used for depositing a silicon-containing film by chemical vapor deposition (CVD) or atomic layer deposition (ALD) at a temperature of 600° C. or higher, and the silicon-containing film can include at least one selected from the group consisting of a silicon-containing oxide film and a silicon-containing composite metal oxide film.

A composition for forming a silicon-containing film according to one embodiment of the present invention comprises a silicon precursor compound represented by the chemical formula 1, thereby forming a silicon-containing film, specifically a silicon-containing oxide film, with excellent coverage and uniformity even on a substrate having a complex shape.

In particular, in the chemical formula 1, since it has a structure in which an amine having excellent surface reactivity and a thermally stable alkyl group are bonded to Si and has a structure containing three Si atoms, it can be more advantageous in forming a high deposition rate and a stable silicon-containing film at a high temperature of about 600°C to 850°C.

That is, in the silicon precursor compound represented by the chemical formula 1, first, in the structure, the amine represented by -NR ₁ R ₂ has excellent reactivity with surfaces such as Si, Si-OH, and Si-O, which is advantageous in forming a silicon-containing oxide film; second, since the structure contains a large number of thermally stable Si and CH ₃ bonds, the silicon precursor does not rapidly decompose at a high temperature of 600° C. or higher and can form a stable film, so that it can be suitable for a 3D NAND flash memory process that requires a dense, excellent covering property, and a uniform silicon-containing film at high temperatures; and third, since the structure contains three Si elements and has a GPC that is significantly larger in SiO ₂ ALD than existing known silicon precursor compounds, it can be suitable for a 3D NAND flash memory process that requires formation of a thick SiO ₂ film at high temperatures.

Specifically, in the chemical formula 1, R ₁ and R ₂ are each independently selected from the group consisting of hydrogen, and a linear or branched C ₁ -C ₄ alkyl group, or R ₁ and R ₂ are directly or indirectly connected to each other to form a substituted or unsubstituted C ₄ -C ₉ cyclic group, wherein the C ₄ -C ₉ cyclic group contains 1 or 2 nitrogens (N) and 0 to 2 oxygens (O).

The above silicon precursor compound may include at least one selected from the group consisting of compounds represented by the following chemical formulas 1-1 to 1-10:

[Chemical Formula 1-1]

,

[Chemical Formula 1-2]

,

[Chemical Formula 1-3]

,

[Chemical Formula 1-4]

,

[Chemical Formula 1-5]

,

[Chemical Formula 1-6]

,

[Chemical Formula 1-7]

,

[Chemical Formula 1-8]

,

[Chemical Formula 1-9]

, and

[Chemical Formula 1-10]

.

According to one embodiment of the present invention, when the silicon-containing film-forming composition is deposited by ALD, the film growth per ALD gas supply cycle (GPC) can be achieved at 1.5 to 4.5 Å/cycle at 600° C. to 850° C.

Specifically, when forming a SiO ₂ film by ALD using the composition for forming a silicon-containing film, the film growth per ALD gas supply cycle can be 1.5 to 4.5 Å/cycle in a temperature range of 600° C. to 850° C.

For example, when the silicon-containing film-forming composition is deposited by ALD, the film growth per ALD gas supply cycle (GPC) can be achieved at a temperature of from 600° C. to 850° C., for example, from 800° C., of from 1.5 to 4.0 Å/cycle, from 1.7 to 4.0 Å/cycle, from 2.0 to 4.0 Å/cycle, from 1.5 to 3.5 Å/cycle, from 1.7 to 3.5 Å/cycle, from 1.5 to 3.0 Å/cycle, or from 2.0 to 3.0 Å/cycle.

According to one embodiment of the present invention, when a silicon-containing film is formed using the composition for forming a silicon-containing film, the film can be controlled to have a desired film thickness and a desired silicon content, and excellent covering properties and a uniform film can be formed even on a substrate having a pattern (groove) on the surface, a porous substrate, a plastic substrate, or a substrate having a complex shape with a three-dimensional structure, so that a high-quality silicon-containing film can be provided.

In addition, using the composition for forming the silicon-containing film, in addition to a silicon-containing film including at least one selected from the group consisting of a silicon-containing oxide film and a silicon-containing composite metal oxide film, at least one selected from the group consisting of a silicon-containing nitride film, a silicon-containing carbide film, and a silicon-containing composite metal film can be efficiently formed on a substrate by CVD or ALD.

In particular, according to one embodiment of the present invention, when a silicon-containing film including at least one selected from the group consisting of a silicon-containing oxide film and a silicon-containing composite metal oxide film is formed on a substrate by ALD using the composition for forming the silicon-containing film, there is a great advantage in that a film having a desired thickness can be obtained with a uniform thickness at a high temperature of 600° C. or higher, and a high-quality silicon-containing film having lower film shrinkage rate and etching rate at high temperatures and less impurities and being pure can be formed.

[silicon precursor compound]

The present invention provides a silicon precursor compound represented by the following chemical formula 0 or the following chemical formula 1:

[Chemical formula 0]

[Chemical Formula 1]

In the above chemical formula 1,

R ₁ and R ₂ are each independently selected from the group consisting of hydrogen and linear or branched C ₁ -C ₄ alkyl groups, or

R ₁ and R ₂ are directly or indirectly linked to each other to form a substituted or unsubstituted C ₄ -C ₉ cyclic group, wherein the C ₄ -C ₉ cyclic group contains 1 or 2 nitrogens (N) and 0 to 2 oxygens (O).

The compounds of the above chemical formulas 0 and 1 can be used in the formation of a silicon-containing film.

Specifically, the compound of the above chemical formula 0 can be used in the production of the compound of the above chemical formula 1, and the composition for forming a silicon-containing film including the compound of the above chemical formula 1 can be used in the deposition of a silicon-containing film.

[Method for producing silicon precursor compound]

Meanwhile, the silicon precursor compound represented by the chemical formula 1 can be manufactured by various methods.

According to one embodiment of the present invention, a method for producing a silicon precursor compound (chemical formula 1) may include a halide-hexamethyldisilazane substitution reaction step in which a hexamethyldisilazane metal salt represented by the following chemical formula A of the following reaction formula 1 is reacted with a dihalide silicon precursor compound represented by the following chemical formula B to form the following chemical formula C, and a halide-amine substitution reaction step in which a compound represented by the following chemical formula C is reacted with a dialkylamine or a cyclic amine represented by the following chemical formula D to form the following chemical formula 1:

[Reaction Formula 1]

In the above reaction formula 1,

M ₁ is an alkali metal, Li or Na,

R ₁ and R ₂ are each independently selected from the group consisting of hydrogen and linear or branched C ₁ -C ₄ alkyl groups, or

R ₁ and R ₂ are directly or indirectly linked to each other to form a substituted or unsubstituted C ₄ -C ₉ cyclic group, wherein the C ₄ -C ₉ cyclic group contains 1 or 2 nitrogens (N) and 0 to 2 oxygens (O),

X ₁ and X ₂ are each independently a halogen element, Cl, Br, or I.

According to another embodiment, the silicon precursor compound of the above chemical formula 1 can be obtained using the silicon precursor compound represented by the following chemical formula 0.

[Chemical formula 0]

Specifically, the silicon precursor compound represented by the chemical formula 1 can be easily synthesized by reacting the silicon precursor compound of the chemical formula 0 with a secondary amine.

The silicon precursor compound of the above chemical formula 0 can be easily synthesized using commercially readily and inexpensively available dichlorosilane (SiH ₂ Cl ₂ ) and hexamethyldisilazane (1,1,1,3,3,3-hexamethyldisilazane) as raw materials. The silicon precursor compound of the above chemical formula 0 can be used for the purpose of producing the silicon precursor compound of the above chemical formula 1.

With reference to the above reaction scheme 1, in order to manufacture the silicon precursor compound (chemical formula 1), 0.5 to 2 mol of a dihalide silicon precursor compound (chemical formula B) may be added to a hexamethyldisilazane metal salt (chemical formula A) at a low temperature (about -30°C to -5°C), and then a substitution reaction between the primary halide and hexamethyldisilazane may be performed. Then, a metal halide salt, which is a reaction by-product included in the reaction product, may be removed through a filter, and the remaining product may be purified, thereby obtaining a compound represented by the above chemical formula C. Thereafter, 1 to 3 mol of a dialkylamine or a cyclic amine (chemical formula D) may be added to the compound represented by the above chemical formula C at a low temperature (about -30°C to -5°C), and then a substitution reaction between the halide and the amine may be performed. Next, the reaction by-product included in the above reaction product, in the form of a dialkylamine halide salt or a cyclic amine halide salt, is removed through a filter, and the remaining product is purified, thereby obtaining a silicon precursor compound represented by the chemical formula 1.

The above primary and secondary halide-amine substitution reactions can each be performed in a solvent at 0°C to 30°C, specifically 20°C to 30°C, for example, at room temperature, for 2 to 30 hours.

Additionally, the solvent may include at least one selected from the group consisting of alkanes having 5 to 8 carbon atoms, toluene, ether, tetrahydrofuran, and mono- to tetraethylene glycol dimethyl ether.

According to one embodiment of the present invention, a composition for forming a silicon-containing film including a silicon precursor compound can be obtained by using the silicon precursor compound.

[silicon-containing membrane]

According to one embodiment of the present invention, a silicon-containing film is provided, formed using a composition for forming a silicon-containing film including a silicon precursor compound represented by the chemical formula 1.

Specifically, a silicon-containing film formed using a composition for forming a silicon-containing film including a silicon precursor compound represented by the chemical formula 1 is provided.

The silicon-containing film may have a thickness of several nanometers (nm) to several micrometers (㎛), and may be applied in various ways depending on the intended application. Specifically, the silicon-containing film may be formed in a thickness range of 1 nm to 500 nm.

The above silicon-containing film can be formed on a substrate (substrate).

The above substrate is as described above.

The above silicon-containing film may include at least one selected from the group consisting of a silicon-containing oxide film and a silicon-containing composite metal oxide film.

In addition, using a composition for forming a silicon-containing film including a silicon precursor compound represented by the chemical formula 1, at least one selected from the group consisting of a silicon-containing oxide film and a silicon-containing composite metal oxide film can be efficiently formed.

In addition, the silicon-containing film is characterized by having a low shrinkage rate of the silicon-containing film and a low etching rate (Å/s) of the silicon-containing film even at a high temperature of 600°C or higher, for example, from 600°C to 850°C, by using a composition for forming a silicon-containing film including a silicon precursor compound having excellent thermal stability.

Specifically, the silicon-containing film may have a shrinkage ratio (S ₇₅₀ ) of 5.0% or less, as represented by the following formula 1:

[Formula 1] Shrinkage rate (S ₇₅₀ , %) = × 100

In the above equation 1,

A is the initial thickness (Å) of the silicon-containing film formed by ALD at 750°C,

B is the thickness (Å) of the silicon-containing film formed by ALD at 750°C after 60 minutes in an argon (Ar) atmosphere at 750°C.

The above silicon-containing film may have a shrinkage ratio (S ₇₅₀ ) of, for example, 4.8% or less, 4.5% or less, 4.4% or less, 4.0% or less, 3.9% or less, 3.8% or less, 3.5% or less, 3.4% or less, 3.3% or less, 3.2% or less, 3.0% or less, 2.5% or less, 2.0% or less, 1.5% or less, 1.2% or less, 1.1% or less, or 1.0% or less. Specifically, the shrinkage ratio (S ₇₅₀ ) of the silicon-containing film represented by the above silicon-containing film may be 4.8% to 0.5%, 3.5% to 0.5%, 3.0% to 0.5%, or 2.5% to 0.5%.

When the above silicon-containing film satisfies the shrinkage rate (S ₇₅₀ ) of the silicon-containing film within the above range, it may be advantageous in forming a uniform and dense silicon-containing film.

Meanwhile, when the silicon-containing film is formed by deposition at 750° C. to a thickness of 500 Å, when the thickness of the silicon-containing film is measured using an ellipsometer before and after exposing the silicon-containing film to an etching solution of 1% dilute hydrofluoric acid, the etching rate (Å/s) of the silicon-containing film expressed by the following Equation 2 may be 4.0 Å/s or less:

[Formula 2] Etching rate (Å/s) = Etching thickness change (ΔE, Å) / 30s

The above etching thickness change (ΔE) can be expressed by the following equation 2-1:

[Formula 2-1] Etching thickness change (ΔE, Å) = E _A - E _B

In the above equation 2-1,

E _A is the initial thickness (Å) of the silicon-containing film formed by ALD at 750°C,

E _B is the thickness (Å) of the silicon-containing film formed by ALD at 750°C after etching in a 1% dilute HF solution for 30 s.

In the above equation 2, “s” means second.

The above silicon-containing film has an etching rate (Å/s) of the silicon-containing film represented by the above formula 2 of, for example, 3.8 Å/s or less, 3.5 Å/s or less, 3.2 Å/s or less, 3.0 Å/s or less, less than 2.9 Å/s, 2.8 Å/s or less, 2.7 Å/s or less, 2.6 Å/s or less, 2.55 Å/s or less, 2.51 Å/s or less, 2.5 Å/s or less, 2.45 Å/s or less, 2.4 Å/s or less, 2.2 Å/s or less, 2.1 Å/s or less, 2.0 Å/s or less, 1.5 Å/s or less, 1.0 Å/s or less, 0.95 Å/s or less, 0.5 Å/s or less, 0.1 Å/s below, 0.05 Å/s or less, or 0.03 Å/s or less.

Specifically, the silicon-containing film has an etching rate (Å/s) of the silicon-containing film represented by the above formula 2 of 3.8 Å/s to 0.5 Å/s, 3.5 Å/s to 0.5 Å/s, 3.0 Å/s to 0.5 Å/s, 2.8 Å/s to 0.5 Å/s, 2.7 Å/s to 0.5 Å/s, 2.6 Å/s to 0.5 Å/s, 2.51 Å/s to 0.5 Å/s, 2.5 Å/s to 0.5 Å/s, 2.1 Å/s to 0.5 Å/s, 2.0 Å/s to 0.5 Å/s, 1.5 Å/s to 0.5 Å/s, 1.2 Å/s to 0.5 Å/s, or It can be between 1.0 Å/s and 0.5 Å/s.

When the above silicon-containing film satisfies the etching rate (Å/s) of the silicon-containing film within the above range, it may be advantageous in forming a uniform and dense silicon-containing film.

In addition, the silicon-containing film may have excellent step coverage.

Specifically, as shown in Fig. 3, after depositing a silicon-containing film on a substrate having a stepped groove pattern, the film is analyzed using a transmission electron microscope (TEM), and the step coverage can be calculated as shown in Equation 3 below.

[Formula 3] Step coverage (%) = B/A x 100 (%)

In the above equation 3

A is the thickness (Å) measured from the top of the home,

B is the thickness (Å) measured from the bottom (floor) of the home.

The silicon-containing film can have a step coverage (%) of, for example, 80% or more, 82% or more, 85% or more, 90% or more, 92% or more, 92.5% or more, 92.9% or more, 93% or more, 95% or more, or 96% or more. As specific examples, the silicon-containing film can have a step coverage (%) of 80% to 99%, 85% to 99%, or 95% to 99%.

Since the step coverage (%) of the above silicon-containing film satisfies the above range, it is easy to control a high step ratio and fine thickness, so that it can be effectively utilized in manufacturing various semiconductor devices such as DRAM and 3D NAND flash memory.

[Example]

The present invention is described more specifically by the following examples. The following examples are intended only to illustrate the present invention, and the scope of the present invention is not limited thereto.

<Example 0> Preparation of chloro-(hexamethyldisilyl)amino-silane : [ClSiH ₂ {N(SiMe ₃ ) ₂ }]

[Chemical formula 0]

In a 20 L round bottom flask, about 910.02 g (2.5 M, about 3.267 mol) of normal butyl lithium hexane solution (n-BuLi in n-hexane) was mixed with about 4,000 mL of anhydrous hexane. About 575.27 g (about 3.564 mol) of hexamethyldisilazane (1,1,1,3,3,3-hexamethyldisilazane) was added at about -20°C, the temperature was gradually raised to room temperature with stirring, and the mixture was stirred for 4 hours. About 330 g (about 3.267 mol) of dichlorosilane was slowly added to the formed lithium (1,1,1,3,3,3-hexamethyldisilazane) salt at -20°C to -10°C, the temperature was gradually raised to room temperature with stirring, and the mixture was stirred for about 17 hours. After completion of the reaction, the salt generated during the reaction was removed through a filtration process, and the solvent and volatile by-products were removed by distillation under reduced pressure to obtain 637 g (yield: 95.00%) of chloro-(hexamethyldisilyl)amino-silane [ClSiH ₂ {N(SiHMe ₃ ) ₂ }], a colorless liquid compound represented by the chemical formula 0, which was used in Examples 1 to 5.

¹ H-NMR(C ₆ D ₆ ): δ 0.165 (N-Si-C H ₃ , s, 18H), δ 5.148 (Si- H ₂ , s, 2H)

<Example 1> Preparation of pyrrolidinyl-(hexamethyldisilyl)amino-silane and a composition for forming a silicon-containing film comprising the same : [(CH ₂ CH ₂ CH ₂ CH ₂ N)SiH ₂ {N(SiMe ₃ ) ₂ }]

[Chemical Formula 1-1]

In a 2 L round bottom flask, about 18.73 g (about 0.083 mol) of chloro-(hexamethyldisilyl)amino-silane obtained in Example 0 was mixed with about 1,000 mL of anhydrous hexane. About 12.97 g (about 0.182 mol) of pyrrolidine was added at about -20°C, and the temperature was gradually raised to room temperature while stirring, and then stirred for about 18 hours. After completion of the reaction, the salt generated during the reaction was removed through a filtration process, and the solvent and volatile by-products were removed by distillation under reduced pressure to obtain 75 g (yield: 74.29%) of pyrrolidinyl-(hexamethyldisilyl)amino-silane [(CH ₂ CH ₂ CH ₂ CH ₂ N)SiH ₂ {N(SiMe ₃ ) ₂ }], a colorless liquid compound represented by the chemical formula 1-1, which was used in a film-forming composition.

b.p: 40℃ at 0.3 torr (223.4℃ at 760torr)

¹ H-NMR(C ₆ D ₆ ): δ 0.268 (N-Si-C H ₃ , s, 18H), δ 1.509 (N-CH ₂ -C H ₂ , m, 4H), δ 2.956 (NC H ₂ -CH _2, m, 4H), δ 4.983 (Si- H ₂ , s, 2H)

<Example 2> Preparation of piperidinyl-(hexamethyldisilyl)amino-silane and a composition for forming a silicon-containing film containing the same : [(CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ N)SiH ₂ {N(SiMe ₃ ) ₂ }]

[Chemical Formula 1-2]

Except for using piperidine instead of pyrrolidine, the same method as in Example 1 was performed to obtain about 53.07 g (yield: about 95%) of a colorless liquid compound piperidinyl-(hexamethyldisilyl)amino-silane represented by the chemical formula 1-2 [(CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ N)SiH ₂ {N(SiMe ₃ ) ₂ }], which was used in a film-forming composition.

b.p: 87℃ at 5.5 torr (227.8℃ at 760torr)

¹ H-NMR(C ₆ D ₆ ): δ 0.268 (N-Si-C H ₃ , s, 18H), δ 1.338 (N-CH ₂ -C H ₂ -CH ₂ , m, 4H), δ 1.432, 1.445 (N-CH ₂ -CH ₂ -C H _2, m, 2H), δ 2.848 (NC H ₂ -CH ₂ -CH _2, t, 4H), δ 4.860 (Si- H ₂ , s, 2H)

<Example 3> Preparation of dimethylamino-(hexamethyldisilyl)amino-silane and a composition for forming a silicon-containing film containing the same : [{(CH ₃ ) ₂ N}SiH ₂ {N(SiMe ₃ ) ₂ }]

[Chemical Formula 1-8]

A colorless liquid compound represented by the chemical formula 1-8, dimethylamino-(hexamethyldisilyl)amino-silane [{(CH ₃ ) ₂ N}SiH ₂ {N(SiMe ₃ ) ₂ }], was obtained in the same manner as in Example 1 except that dimethylamine was used instead of pyrrolidine (yield: about 85%), which was used in a film-forming composition.

b.p: 69℃ at 13 torr (186.5℃ at 760torr)

¹ H-NMR(C ₆ D ₆ ): δ 0.242 (N-Si-C H ₃ , s, 18H), δ 2.407 (NC H ₃ , s, 6H), δ 4.837 (Si- H _2, s, 2H)

<Example 4> Preparation of ethylmethylamino-(hexamethyldisilyl)amino-silane and a composition for forming a silicon-containing film containing the same : [{(CH ₃ CH ₂ )(CH ₃ )N}SiH ₂ {N(SiMe ₃ ) ₂ }]

[Chemical Formula 1-9]

A colorless liquid compound represented by the chemical formula 1-9, ethylmethylamino-(hexamethyldisilyl)amino-silane [{(CH 3 CH ₂ )(CH ₃ )N}SiH ₂ {N(SiMe _{3 ) 2} }], was obtained in the same manner as in Example 1, except that ethylmethylamine was used instead of pyrrolidine, in an amount of about 175.12 g (yield: about 79.6%), which was used in a film-forming composition.

b.p: 68℃ at 9 torr (192.1℃ at 760torr)

¹ H-NMR(C ₆ D ₆ ): δ 0.255 (N-Si-C H ₃ , s, 18H), δ 0.973 (N-CH ₂ -C H ₃ , t, 3H), δ 2.417 (NC H ₃ , s, 3H) 2.785 2.767 (NC H ₂ -CH ₃ , q, 2H), δ 4.873 (Si- H _2, s, 2H)

<Example 5> Preparation of diethylamino-(hexamethyldisilyl)amino-silane and a composition for forming a silicon-containing film containing the same : [{(CH ₃ CH ₂ ) ₂ N}SiH ₂ {N(SiMe ₃ ) ₂ }]

[Chemical Formula 1-10]

A colorless liquid compound diethylamino-(hexamethyldisilyl)amino-silane [{(CH 3 CH 2 ) 2 N}SiH ₂ { _N (SiMe _{3 ) 2} }] represented by the chemical formula 1-10 was obtained in the same manner _as in Example 1 except that diethylamine was used instead of pyrrolidine (about 41.6 g (yield: about 79.5%), which was used in a film-forming composition.

b.p: 75℃ at 6 torr (210℃ at 760torr)

¹ H-NMR(C ₆ D ₆ ): δ 0.266 (N-Si-C H ₃ , s, 18H), δ 0.979 (N-CH ₂ -C H ₃ , t, 6H), δ 2.854 2.837 (NC H ₂ -CH _3, q, 4H), δ 4.891 (Si- H _2, s, 2H)

Comparative Example 1

Tris(dimethylamino)silane (3DMAS or TDMAS) [SiH( _NMe2 ) ₃ ] (product of U-P Chemical Co., Ltd.) was used.

Comparative Example 2

Preparation of pyrrolidinyl-(tetramethyldisilyl)amino-silane and a composition for forming a silicon-containing film comprising the same : [(CH ₂ CH ₂ CH ₂ CH ₂ N)SiH ₂ {N(SiHMe ₂ ) ₂ }]

[Chemical Formula 1-11]

Except that tetramethyldisilazane (1,1,3,3-tetramethyldisilazane) was used instead of hexamethyldisilazane (1,1,1,3,3,3-hexamethyldisilazane), the same method as in Example 1 was repeated to obtain about 38 g (yield: about 65%) of a colorless liquid compound pyrrolidinyl-(tetramethyldisilyl)amino-silane [(CH ₂ CH ₂ CH ₂ CH ₂ N)SiH ₂ {N(SiHMe ₂ ) ₂ }] represented by the chemical formula 1-11, which was used in a film-forming composition.

b.p: 32℃ at 0.3 torr (210.3℃ at 760torr)

¹ H-NMR(C ₆ D ₆ ): δ 0.265, 0.273 (N-Si-C H ₃ , d, 12H), δ 1.502 (N-CH ₂ -C H ₂ , m, 4H), δ 2.973 (NC H _2, m, 4H), δ 4.827 (N-Si- H _, m, 2H), δ 4.981 (Si- H ₂ , s, 2H)

[Experimental example]

<Experimental Example 1> Analysis of high-temperature deposition characteristics of a composition for forming a silicon-containing film containing a silicon precursor compound

A silicon-containing film was formed by ALD using a composition for forming a silicon-containing film including the silicon precursor compounds of Examples 1 and 3 and Comparative Examples 1 and 2, and ozone (O ₃ ) as a reaction gas.

First, a silicon substrate was immersed in a Piranha solution containing sulfuric acid ( _H2SO4 ) and _hydrogen peroxide ( _H2O2 ) in a 4:1 _ratio for about 10 minutes, then taken out and immersed in a dilute HF aqueous solution for 2 minutes to form a pure surface. A silicon-containing oxide film was formed on the silicon substrate by ALD.

The compositions for forming a silicon-containing film including the silicon precursor compounds of Examples 1 and 3 and Comparative Examples 1 and 2 were placed in a stainless steel container and used at room temperature or after heating. Comparative Example 1 was used at room temperature without heating, and Examples 1, 3 and Comparative Example 2 were used after heating to 60°C. The process pressure of the reactor was set to 4 torr, and argon (Ar) carrier gas was flowed at a flow rate of about 200 sccm to supply the film-forming composition in a gaseous state to the reaction chamber.

In order to confirm the deposition characteristics of each silicon-containing oxide film, a silicon-containing oxide film was formed by repeating the gas supply cycle 100 times, in which a film-forming composition was supplied in a gaseous state for about 3 seconds → argon (Ar) gas was supplied for about 10 seconds to remove the film-forming composition (gas) remaining in the reactor → ozone (O ₃ ) was supplied as a reaction gas for about 5 seconds → argon (Ar) gas was supplied for about 10 seconds to remove the ozone (O ₃ ) gas remaining in the reactor.

The thickness of each oxide film formed using the silicon-containing film-forming composition manufactured by the method of the above examples and comparative examples was measured using an ellipsometer (J.A. Woollam, M-2000).

Thereafter, the measured thickness was divided by the number of gas supply cycles (100 times) to measure the film growth per ALD gas supply cycle (GPC).

Specifically, film growth (GPC) per ALD gas supply cycle was measured at temperatures (process temperatures) of 600°C to 850°C, and the results are shown in Fig. 1 and Table 1.

Deposition
temperature
(℃) Film growth per ALD gas supply cycle (Å/cycle) Example 1 Example 3 Comparative Example 1 Comparative Example 2 Chemical Formula 1-1 Chemical Formula 1-8 3DMAS Chemical Formula 1-11 600 1.95 2.33 0.62 1.76 650 2.16 2.55 0.64 2.59 700 2.23 - 0.71 3.33 750 2.23 2.54 0.88 4.13 800 2.06 2.54 2.97 5.15 850 1.99 3.55 13.78 12.57

As can be seen in Table 1 and FIG. 1, when performing ALD at a high temperature of 600°C or higher using the silicon-containing film-forming compositions including the silicon precursor compounds of Examples 1 and 3, it was found that GPC was constant up to a relatively high temperature of 600°C or higher and 850°C, compared to the case where the silicon-containing film-forming compositions including the silicon precursor compounds of Comparative Examples 1 and 2 were used.

Specifically, when the silicon-containing film-forming composition including the silicon precursor compound of Comparative Example 1 was used, the film growth (GPC) per ALD gas supply cycle increased from about 700°C, and when the silicon-containing film-forming composition including the silicon precursor compound of Comparative Example 2 was used, the film growth (GPC) per ALD gas supply cycle increased from about 650°C, whereas when the silicon-containing film-forming composition including the silicon precursor compounds of Examples 1 and 3 were used, the film growth (GPC) per ALD gas supply cycle was constant even at a high temperature of 800°C or 850°C. From this, it can be confirmed that the silicon-containing film-forming composition including the silicon precursor compound of the examples of the present invention is a precursor suitable for a high-temperature ALD process because it exhibits a constant GPC and self-limiting film growth characteristics at high temperatures of 600°C to 800°C or 850°C.

<Experimental Example 2> Analysis of physical properties of high-temperature deposited silicon-containing oxide film

The physical and chemical properties of SiO ₂ films formed at the same thickness on a flat wafer at 750° C. by controlling the ALD gas supply cycle using a composition for forming a silicon-containing film including the silicon precursor compounds of Examples 1, 3 and Comparative Example 1 were analyzed.

Specifically, the shrinkage and wet etch rate (WER, Å/s) of the SiO ₂ film were measured. The thickness of the SiO ₂ film was measured using an ellipsometer (JA Woollam, M-2000).

The thickness of a silicon-containing film (SiO ₂ film) formed with an initial thickness of approximately 100 Å on a flat wafer at 750°C by controlling the ALD gas supply cycle as shown in Table 2 below was compared with the thickness of a silicon-containing film (SiO ₂ film) after annealing at 750°C for 60 minutes in an argon (Ar) atmosphere, and the shrinkage using Equation 1 below was calculated.

[Formula 1] Shrinkage rate (S ₇₅₀ , %) = × 100

In the above equation 1,

A is the initial thickness (Å) of the silicon-containing film formed by ALD at 750°C,

B is the thickness (Å) of the silicon-containing film formed by ALD at 750°C after 60 minutes in an argon (Ar) atmosphere at 750°C.

The results are shown in Table 2.

Example 1 Example 3 Comparative Example 1 compound Chemical Formula 1-1 Chemical Formula 1-8 3DMAS Initial thickness (Å) of SiO ₂ films formed by ALD at 750°C (A) 101.32 103.41 101.80 Thickness (Å) of SiO ₂ film formed by ALD at 750°C after 60 min residence at 750°C (B) 97.92 100.97 95.28 Shrinkage (S ₇₅₀ , %) 3.34 2.36 6.40

As can be seen in Table 2 above, the shrinkage rates of the silicon-containing oxide films (SiO ₂ films) deposited using the silicon-containing film-forming compositions of Examples 1 and 3 were 3.34% and 2.36%, respectively, whereas the shrinkage rate of the silicon-containing oxide film deposited using the silicon-containing film-forming composition of Comparative Example 1 was 6.40%. As such, the silicon-containing oxide films deposited using the silicon-containing film-forming compositions of Examples 1 and 3 had lower film shrinkage rates at high temperatures than the silicon-containing oxide films deposited using the silicon-containing film-forming composition of Comparative Example 1.

Meanwhile, a silicon-containing film (SiO ₂ film) was formed with an initial thickness of approximately 500 Å on a flat wafer at 750°C by controlling the ALD gas supply cycle as shown in Table 3 below, and was etched in a 1% dilute HF solution for 30 seconds, and the thickness change was measured to calculate the etching rate (WER, wet etch rate, Å/s) using Equation 2 below.

[Formula 2] Etching rate (Å/s) = Etching thickness change (ΔE, Å) / 30s

The above etching thickness change (ΔE) can be expressed by the following equation 2-1:

[Formula 2-1] Etching thickness change (ΔE, Å) = E _A - E _B

In the above equation 2-1,

E _A is the initial thickness (Å) of the silicon-containing film formed by ALD at 750°C,

E _B is the thickness (Å) of the silicon-containing film formed by ALD at 750°C after etching in a 1% dilute HF solution for 30 s.

In the above equation 2, “s” means second.

The results are shown in Table 3 below.

Example 3 Comparative Example 1 compound Chemical Formula 1-8 3DMAS Initial thickness (Å) of SiO ₂ films formed by ALD at 750°C (E _A ) 497.0 503.4 Thickness (Å) of silicon-containing film after etching of SiO ₂ film formed by ALD at 750°C for 30 s in 1% dilute HF solution (E _B ) 421.7 416.4 Etch rate (E _A - E _B )/30s (Å/s) 2.51 2.90

As can be seen in Table 3 above, the etching rate of the silicon-containing oxide film (SiO ₂ film) deposited using the silicon-containing film-forming composition of Example 3 was 2.51 Å/s, whereas the etching rate of the silicon-containing oxide film deposited using the silicon-containing film-forming composition of Comparative Example 1 was 2.90 Å/s, confirming that the etching rate (Å/s) of the silicon-containing oxide film formed using the silicon-containing film-forming composition of Example 3 decreased.

Meanwhile, in order to confirm the impurities in the silicon-containing oxide film, secondary ion mass spectrometry (SIMS) of the silicon-containing oxide film was measured.

FIG. 2 is a graph showing the results of secondary ion mass spectrometry (SIMS) of a silicon-containing oxide film deposited at 750° C. using the silicon-containing film-forming compositions of Example 3 and Comparative Example 1 of the present invention.

To confirm the impurities in the silicon-containing oxide film deposited using the silicon-containing film forming compositions of Comparative Example 1 and Example 3, the carbon (C) component of the silicon-containing oxide film deposited to about 100 Å was analyzed using SIMS.

As a result, it was found that the content of carbon components was reduced by about 40.6% in Example 3 compared to Comparative Example 1, and it was confirmed that a pure silicon-containing oxide film with less than 100 Counts of carbon components was formed.

FIG. 3 is a transmission electron microscope (TEM) image of a silicon-containing oxide film formed on a substrate having a deep groove pattern at 750° C. by ALD using the silicon-containing film-forming compositions of Examples 1 and 3 and Comparative Example 1 of the present invention and ozone (O ₃ ). The thicknesses of the silicon-containing oxide films measured at the portions indicated in FIG. 3 are shown in Table 4.

Example 1 Example 3 Comparative Example 1 compound Chemical Formula 1-1 Chemical Formula 1-8 3DMAS Thickness (Å) measured from the top of the home (A) 110.8 98.5 82.0 Thickness (Å) measured at the break of the home 108.5 97.3 78.6 Thickness (Å) measured from the bottom (floor) of the home (B) 107.0 96.4 69.1 Step coverage (%) (B/A × 100 (%)) 96.6% 97.8% 84.3%

As can be confirmed in Table 4 above, when the silicon-containing film-forming compositions of Examples 1, 3 and Comparative Example 1 were deposited on a substrate with steps and analyzed using TEM, the step coverage (%) of the silicon-containing oxide films deposited using the silicon-containing film-forming compositions of Examples 1 and 3 was 96.6 and 97.8%, respectively, whereas the step coverage (%) of the silicon-containing oxide film deposited using the silicon-containing film-forming composition of Comparative Example 1 was 84.3%, showing that the step coverage of the silicon-containing oxide films formed using the silicon-containing film-forming compositions of Examples 1 and 3 was far superior to the step coverage of the silicon-containing oxide film formed using the silicon-containing film-forming composition of Comparative Example 1.

FIG. 4 is a transmission electron microscope (TEM) image of a silicon-containing oxide film formed at 650° C. on a substrate having a deep groove pattern using the silicon-containing film-forming composition of Example 3 and Comparative Example 1 of the present invention and ozone (O ₃ ) by ALD. The thicknesses of the silicon-containing oxide films measured at the portions indicated in FIG. 4 are shown in Table 5.

Example 3 Comparative Example 1 compound Chemical Formula 1-8 3DMAS Thickness (Å) measured from the top of the home (A) 106.9 105.3 Thickness (Å) measured at the break of the home 103.9 102.4 Thickness (Å) measured from the bottom (floor) of the home (B) 106.7 96.2 Step coverage (%) (B/A × 100 (%)) 99.8% 91.4%

As can be confirmed in Table 5 above, when the silicon-containing film-forming compositions of Example 3 and Comparative Example 1 were deposited on a substrate with steps and analyzed using TEM, the step coverage (%) of the silicon-containing oxide film deposited using the silicon-containing film-forming composition of Example 3 was 99.8%, whereas the step coverage (%) of the silicon-containing oxide film deposited using the silicon-containing film-forming composition of Comparative Example 1 was 91.4%, showing that the step coverage of the silicon-containing oxide film formed using the silicon-containing film-forming composition of Example 3 was far superior to the step coverage of the silicon-containing oxide film formed using the silicon-containing film-forming composition of Comparative Example 1.

It can be expected that the silicon-containing oxide film formed at a temperature of 600°C or higher using a composition including not only the silicon compounds of Chemical Formulas 1-1 and 1-8 but also other silicon compounds of Chemical Formula 1 will have superior shrinkage rate, etching rate, carbon component content of the film, and step coverage than the silicon-containing oxide film formed using the composition of Comparative Example 1.

In summary, according to the method for forming a silicon-containing film using a composition for forming a silicon-containing film including a silicon precursor compound according to one embodiment of the present invention, not only can a silicon-containing film be easily deposited by ALD, but the thickness and composition of the film can be precisely controlled, and a film with excellent coverage and uniformity can be formed even on a substrate of complex shape.

In particular, according to the method for forming a silicon-containing film using the composition for forming a silicon-containing film including the silicon precursor compound of the present invention, a film having a desired thickness can be obtained at a high temperature of 600° C. to 850° C. during deposition, and it can be seen that the physical properties of the silicon-containing oxide film thus obtained, such as step coverage, shrinkage rate, and etching rate, are significantly improved compared to the silicon-containing oxide film using the composition for forming a silicon-containing film including the silicon precursor compound of Comparative Example 1.

Claims (15)

A step of depositing a silicon-containing film at 600° C. or higher using a composition for forming a silicon-containing film including a silicon precursor compound represented by the following chemical formula 1,
A step of supplying the silicon precursor compound into the reaction chamber using a method including at least one selected from the group consisting of a bubbling method, a liquid delivery system (LDS) method, a vapor flow control (VFC) method, and a bypass method,
The step of supplying into the above reaction chamber is performed using a carrier gas or dilution gas in a temperature range of 0.1 torr to 10 torr and room temperature to 150°C,
A method for forming a silicon-containing film, wherein the carrier gas or diluting gas comprises at least one gas selected from the group consisting of argon (Ar), nitrogen (N ₂ ), helium (He), and hydrogen (H ₂ ).
[Chemical Formula 1]

In the above chemical formula 1,
R ₁ and R ₂ are each independently selected from the group consisting of hydrogen and linear or branched C ₁ -C ₄ alkyl groups, or
R ₁ and R ₂ are directly or indirectly linked to each other to form a substituted or unsubstituted C ₄ -C ₉ cyclic group, wherein the C ₄ -C ₉ cyclic group contains 1 or 2 nitrogens (N) and 0 to 2 oxygens (O).
In paragraph 1,
A method for forming a silicon-containing film, wherein the silicon precursor compound comprises at least one selected from the group consisting of compounds represented by the following chemical formula:
, , , , , , , , , and .
In the first paragraph,
A method for forming a silicon-containing film, wherein the silicon-containing film is formed by chemical vapor deposition (CVD) or atomic layer deposition (ALD) at a temperature of 600°C to 850°C.
In paragraph 1,
A method for forming a silicon-containing film, wherein when forming a SiO ₂ film by atomic layer deposition (ALD) using the composition for forming the silicon-containing film, the film growth per ALD gas supply cycle is 1.5 to 4.5 Å/cycle in a temperature range of 600°C to 850°C.
delete delete In the first paragraph,
A method for forming a silicon-containing film, wherein thermal energy or plasma is used during the above deposition, or a bias is applied to the substrate.
In the first paragraph,
The above silicon-containing film comprises at least one selected from the group consisting of a silicon-containing oxide film and a silicon-containing composite metal oxide film,
A method for forming a silicon-containing film, wherein, during the above deposition _, at least one selected from the group consisting of water vapor (H _{2 O} ), oxygen (O ₂ ), oxygen plasma (O ₂ Plasma), hydrogen peroxide (H 2 O 2 ), and ozone (O ₃ ) is used.
In paragraph 1,
A method for forming a silicon-containing film, wherein the silicon-containing film is formed in a thickness range of 1 nm to 500 nm.
In the first paragraph,
A method for forming a silicon-containing film, wherein the silicon-containing film is formed on a substrate including at least one unevenness having an aspect ratio of 1 or more and a width of 1 ㎛ or less.
A composition for forming a silicon-containing film, comprising a silicon precursor compound represented by the following chemical formula 1 and used for depositing a silicon-containing film:
[Chemical Formula 1]

In the above chemical formula 1,
R ₁ and R ₂ are each independently selected from the group consisting of hydrogen and linear or branched C ₁ -C ₄ alkyl groups, or
R ₁ and R ₂ are directly or indirectly linked to each other to form a substituted or unsubstituted C ₄ -C ₉ cyclic group, wherein the C ₄ -C ₉ cyclic group contains 1 or 2 nitrogens (N) and 0 to 2 oxygens (O).
In Article 11,
A composition for forming a silicon-containing film, wherein the silicon precursor compound comprises at least one compound selected from the group consisting of compounds represented by the following chemical formula:
, , , , , , , , , and .
A silicon precursor compound represented by the following chemical formula 0:
[Chemical formula 0]

A silicon precursor compound represented by the following chemical formula 1:
[Chemical Formula 1]

In the above chemical formula 1,
R ₁ and R ₂ are each independently selected from the group consisting of hydrogen and linear or branched C ₁ -C ₄ alkyl groups, or
R ₁ and R ₂ are directly or indirectly linked to each other to form a substituted or unsubstituted C ₄ -C ₉ cyclic group, wherein the C ₄ -C ₉ cyclic group contains 1 or 2 nitrogens (N) and 0 to 2 oxygens (O).
In Article 14,
A compound wherein the silicon precursor compound is selected from the group consisting of compounds represented by the following chemical formula:
, , , , , , , , , and .